Compositions comprising 2,3-dichloro-1,1,1-trifluoropropane, 2-chloro-1,1,1-trifluoropropene, 2-chloro-1,1,1,2-tetrafluoropropane or 2,3,3,3-tetrafluoropropene

ABSTRACT

Disclosed are compositions comprising HCFC-243db, HCFO-1233xf, HCFC-244db and/or HFO-1234yf and at least one additional compound. For the composition comprising 1234yf, the additional compound is selected from the group consisting of HFO-1234ze, HFO-1243zf, HCFC-243db, HCFC-244db, HFC-245cb, HFC-245fa, HCFO-1233xf, HCFO-1233zd, HCFC-253fb, HCFC-234ab, HCFC-243fa, ethylene, HFC-23, CFC-13, HFC-143a, HFC-152a, HFC-236fa, HCO-1130, HCO-1130a, HFO-1336, HCFC-133a, HCFC-254fb, CHF═CHCl, HFO-1141, HCFO-1242zf, HCFO-1223xd, HCFC-233ab, HCFC-226ba, and HFC-227ca. Compositions comprising HCFC-243db, HCFO-1233xf, and/or HCFC-244db are useful in processes to make HFO-1234yf. Compositions comprising HFO-1234yf are useful, among other uses, as heat transfer compositions for use in refrigeration, air-conditioning and heat pump systems.

BACKGROUND Field of the Invention

The present disclosure relates to the field of compositions which may beuseful as heat transfer compositions, aerosol propellants, foamingagents, blowing agents, solvents, cleaning agents, carrier fluids,displacement drying agents, buffing abrasion agents, polymerizationmedia, expansion agents for polyolefins and polyurethane, gaseousdielectrics, extinguishing agents, and fire suppression agents in liquidor gaseous form. In particular, the present disclosure relates tocompositions which may be useful as heat transfer compositions, such as2,3,3,3,-tetrafluoropropene (HFO-1234yf, or 1234yf) or compositionscomprising 2,3-dichloro-1,1,1-trifluoropropane (HCFC-243db or 243db),2-chloro-1,1,1-trifluoropropene (HCFO-1233xf or 1233xf) or2-chloro-1,1,1,2-tetrafluoropropane (HCFC-244bb).

2. Description of Related Art

New environmental regulations have led to the need for new compositionsfor use in refrigeration, air-conditioning and heat pump apparatus. Lowglobal warming potential compounds are of particular interest.

SUMMARY OF THE INVENTION

Applicants have found that in preparing such new low global warmingpotential compounds, such as 1234yf, that certain additional compoundsare present in small amounts.

Therefore, in accordance with the present invention, there is provided acomposition comprising HFO-1234yf and at least one additional compoundselected from the group consisting of HFO-1234ze, HFO-1243zf,HCFC-243db, HCFC-244db, HFC-245cb, HFC-245fa, HCFO-1233xf, HCFO-1233zd,HCFC-253fb, HCFC-234ab, HCFC-243fa, ethylene, HFC-23, CFC-13, HFC-143a,HFC-152a, HFO-1243zf, HFC-236fa, HCO-1130, HCO-1130a, HFO-1336,HCFC-133a, HCFC-254fb, HCFC-1131, HFC-1141, HCFO-1242zf, HCFO-1223xd,HCFC-233ab, HCFC-226ba, and HFC-227ca. The composition contains lessthan about 1 weight percent of the at least one additional compound.

Compositions comprising HCFC-243db, HCFO-1233xf, and/or to HCFC-244dbare useful in processes to make HFO-1234yf. Therefore, compositionscomprising 1234yf may contain some amount of HCFC-243db, HCFO-1233xf,and/or HCFC-244db, in addition to other compounds.

Therefore, in accordance with the present invention, there is provided acomposition comprising HCFC-243db and at least one additional compoundselected from the group consisting of ethylene, HFC-23, CFC-13,HFC-143a, HFC-152a, HFO-1234yf, HFO-1243zf, HFC-236fa, HCO-1130,HCO-1130a, HFO-1234ze, HFO-1336, HCFC-244bb, HCFC-244db, HFC-245fa,HFC-245cb, HCFC-133a, HCFC-254fb, HCFC-1131, HCFO-1233xf, HCFO-1233zd,HCFO-1242zf, HCFC-253fb, HCFO-1223xd, HCFC-233ab, HCFC-226ba, andHFC-227ca. The composition may contain anywhere from greater than zeroweight percent to about 99 weight percent of HCFC-243db.

In addition, in accordance with the present invention, there is furtherprovided a composition comprising HCFO-1233xf and at least oneadditional compound selected from the group consisting of HCFO-1233zd,HCFO-1232xd, HCFO-1223xd, HCFC-253fb, HCFC-233ab, HFO-1234yf,HFO-1234ze, ethylene, HFC-23, CFC-13, HFC-143a, HFC-152a, HFO-1243zf,HFC-236fa, HCO-1130, HCO-1130a, HFO-1336, HCFC-244bb, HCFC-244db,HFC-245fa, HFC-245cb, HCFC-133a, HCFC-254fb, HCFC-1131, HCFO-1242zf,HCFO-1223xd, HCFC-233ab, HCFC-226ba, and HFC-227ca. The composition maycontain anywhere from greater than zero weight percent to about 99weight percent of HCFO-1233xf.

In addition, in accordance with the present invention, there is alsoprovided a composition comprising HCFC-244bb and at least one additionalcompound selected from the group consisting of HCFO-1233zd, HCFO-1232xd,HCFO-1223xd, HCFC-253fb, HCFC-233ab, HFO-1234yf, HFO-1234ze, ethylene,HFC-23, CFC-13, HFC-143a, HFC-152a, HFO-1243zf, HFC-236fa, HCO-1130,HCO-1130a, HFO-1336, HCFC-244db, HFC-245fa, HFC-245cb, HFC-245eb,HCFC-133a, HCFC-254fb, HCFC-1131, HCFO-1242zf, HCFO-1223xd, HCFC-233ab,HCFC-226ba, and HFC-227ca. The composition may contain anywhere fromgreater than zero weight percent to about 99 weight percent ofHCFC-244bb.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic drawing showing a reaction for producingHFO-1234yf from 243db.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

HFO-1234yf has been suggested for use as a refrigerant, heat transferfluid, aerosol propellant, foam expansion agent, among other uses. Ithas also, advantageously, been found that HFO-1234yf has a low globalwarming potential (GWP) as reported by V. C. Papadimitriou, et al. inPhysical Chemistry Chemical Physics, 2007, volume 9, pages 1-13. Thus,HFO-1234yf is a good candidate for replacing the higher GWP saturatedHFC refrigerants.

In one embodiment, the present disclosure provides a compositioncomprising HFO-1234yf and at least one additional compound selected fromthe group consisting of HFO-1234ze, HFO-1243zf, HCFC-243db, HCFC-244db,HFC-245cb, HFC-245fa, HCFO-1233xf, HCFO-1233zd, HCFC-253fb, HCFC-234ab,HCFC-243fa, ethylene, HFC-23, CFC-13, HFC-143a, HFC-152a, HFC-236fa,HCO-1130, HCO-1130a, HFO-1336, HCFC-133a, HCFC-254fb, HCFC-1131,HFO-1141, HCFO-1242zf, HCFO-1223xd, HCFC-233ab, HCFC-226ba, HFC-227ca.

In one embodiment, the total amount of additional compound(s) in thecomposition comprising HFO-1234yf ranges from greater than zero weightpercent to less than 1 weight percent.

In some embodiments, the impurities present in the HCFC-243db,HCFO-1233xf, and HCFC-244bb will remain intact during the reaction tomake HFO-1234yf, thus they are included in the additional compounds.

In another embodiment, the present disclosure provides a compositioncomprising HCFC-243db and at least one additional compound selected fromthe group consisting of ethylene, HFC-23, CFC-13, HFC-143a, HFC-152a,HFO-1234yf, HFO-1243zf, HFC-236fa, HCO-1130, HCO-1130a, HFO-1234ze,HFO-1336, HCFC-244bb, HCFC-244db, HFC-245fa, HFC-245cb, HCFC-133a,HCFC-254fb, HCFC-1131, HCFO-1233xf, HCFO-1233zd, HCFO-1242zf,HCFC-253fb, HCFO-1223xd, HCFC-233ab, HCFC-226ba, and HFC-227ca.

In one embodiment, the total amount of additional compound(s) in thecomposition comprising HCFC-243db ranges from greater than zero weightpercent to about 99 weight percent. In another embodiment, the totalamount of additional compounds ranges from about 1 weight percent toabout 80 weight percent. In another embodiment, the total amount ofadditional compound(s) ranges from about 1 weight percent to about 50weight percent. In another embodiment, the total amount of additionalcompound(s) ranges from about 1 weight percent to about 30 weightpercent. In another embodiment, the total amount of additionalcompound(s) ranges from about 1 weight percent to about 10 weightpercent.

In some embodiments, certain precursor compounds to HCFC-243db containimpurities that appear in the HCFC-243db. In other embodiments, theadditional compounds are formed by reaction of these precursorimpurities. In other embodiments, the reaction conditions under whichthe HCFC-243db is produced also produce by-products, by which is meantalternative reaction pathways may produce additional compounds dependingupon the particular conditions under which the HCFC-243db is produced.

In another embodiment, the present disclosure provides a compositioncomprising HCFO-1233xf and at least one additional compound selectedfrom the group consisting of HCFO-1233zd, HCFO-1232xd, HCFO-1223xd,HCFC-253fb, HCFC-233ab, HFO-1234yf, HFO-1234ze, ethylene, HFC-23,CFC-13, HFC-143a, HFC-152a, HFO-1243zf, HFC-236fa, HCO-1130, HCO-1130a,HFO-1336, HCFC-244bb, HCFC-244db, HFC-245fa, HFC-245cb, HCFC-133a,HCFC-254fb, HCFC-1131, HCFO-1242zf, HCFO-1223xd, HCFC-233ab, HCFC-226ba,HFC-227ca.

In one embodiment, the total amount of additional compound(s) in thecomposition comprising HCFO-1233xf ranges from greater than zero weightpercent to about 99 weight percent. In another embodiment, the totalamount of additional compounds ranges from about 1 weight percent toabout 80 weight percent. In another embodiment, the total amount ofadditional compound(s) ranges from about 1 weight percent to about 50weight percent. In another embodiment, the total amount of additionalcompound(s) ranges from about 1 weight percent to about 30 weightpercent. In another embodiment, the total amount of additionalcompound(s) ranges from about 1 weight percent to about 10 weightpercent.

In some embodiments, certain precursor compounds to HCFO-1233xf containimpurities that appear in the HCFO-1233xf. In other embodiments, theadditional compounds are formed by reaction of these precursorimpurities. In other embodiments, the reaction conditions under whichthe HCFO-1233xf is produced also produce by-products, by which is meantalternative reaction pathways may produce additional compounds dependingupon the particular conditions under which the HCFO-1233xf is produced.

In another embodiment, the present disclosure provides a compositioncomprising HCFC-244bb and at least one additional compound selected fromthe group consisting of HCFO-1233zd, HCFO-1232xd, HCFO-1223xd,HCFC-253fb, HCFC-233ab, HFO-1234yf, HFO-1234ze, ethylene, HFC-23,CFC-13, HFC-143a, HFC-152a, HFO-1243zf, HFC-236fa, HCO-1130, HCO-1130a,HFO-1336, HCFC-244db, HFC-245fa, HFC-245cb, HFC-245eb, HCFC-133a,HCFC-254fb, HCFC-1131, HCFO-1242zf, HCFO-1223xd, HCFC-233ab, HCFC-226ba,HFC-227ca.

In one embodiment, the total amount of additional compound(s) in thecomposition comprising HCFC-244bb ranges from greater than zero weightpercent to about 99 weight percent. In another embodiment, the totalamount of additional compounds ranges from about 1 weight percent toabout 80 weight percent. In another embodiment, the total amount ofadditional compound(s) ranges from about 1 weight percent to about 50weight percent. In another embodiment, the total amount of additionalcompound(s) ranges from about 1 weight percent to about 30 weightpercent. In another embodiment, the total amount of additionalcompound(s) ranges from about 1 weight percent to about 10 weightpercent.

In some embodiments, certain precursor compounds to HCFC-244bb containimpurities that appear in the HCFC-244bb. In other embodiments, theadditional compounds are formed by reaction of these precursorimpurities. In other embodiments, the reaction conditions under whichthe HCFC-244bb is produced also produce by-products that then appear inthe HCFC-243db compositions, by which is meant alternative reactionpathways may produce additional compounds depending upon the particularconditions under which the HCFC-244bb is produced.

The compositions disclosed herein comprising HFO-1234yf are useful aslow global warming potential (GWP) heat transfer compositions, aerosolpropellant, foaming agents, blowing agents, solvents, cleaning agents,carrier fluids, displacement drying agents, buffing abrasion agents,polymerization media, expansion agents for polyolefins and polyurethane,gaseous dielectrics, extinguishing agents, and fire suppression agentsin liquid or gaseous form. The disclosed compositions can act as aworking fluid used to carry heat from a heat source to a heat sink. Suchheat transfer compositions may also be useful as a refrigerant in acycle wherein the fluid undergoes a phase change; that is, from a liquidto a gas and back or vice versa.

Examples of heat transfer systems include but are not limited to airconditioners, freezers, refrigerators, heat pumps, water chillers,flooded evaporator chillers, direct expansion chillers, walk-in coolers,heat pumps, mobile refrigerators, mobile air conditioning units andcombinations thereof.

As used herein, mobile refrigeration apparatus, mobile air conditioningor mobile heating apparatus refers to any refrigeration, airconditioner, or heating apparatus incorporated into a transportationunit for the road, rail, sea or air. In addition, mobile refrigerationor air conditioner units, include those apparatus that are independentof any moving carrier and are known as “intermodal” systems. Suchintermodal systems include “containers’ (combined sea/land transport) aswell as “swap bodies” (combined road/rail transport).

As used herein, stationary heat transfer systems are systems associatedwithin or attached to buildings of any variety. These stationaryapplications may be stationary air conditioning and heat pumps(including but not limited to chillers, high temperature heat pumps,residential, commercial or industrial air conditioning systems, andincluding window, ductless, ducted, packaged terminal, chillers, andthose exterior but connected to the building such as rooftop systems).In stationary refrigeration applications, the disclosed compositions maybe useful in equipment including commercial, industrial or residentialrefrigerators and freezers, ice machines, self-contained coolers andfreezers, flooded evaporator chillers, direct expansion chillers,walk-in and reach-in coolers and freezers, and combination systems. Insome embodiments, the disclosed compositions may be used in supermarketrefrigerator systems.

The compounds making up the disclosed compositions are defined in Table1.

TABLE 1 Code Structure Chemical name CH₂═CH₂ Ethylene CFC-13 CF₃Clchlorotrifluoromethane HFC-23 CHF₃ trifluoromethane HCFC-133a CF₃CH₂Cl2-chloro-1,1,1-trifluoroethane HFO-134 CHF₂CHF₂1,1,2,2-tetrafluoroethane HFO-134a CF₃CH₂F 1,1,1,2-tetrafluoroethaneHFC-143a CF₃CH₃ 1,1,1-trifluoroethane HFC-152a CHF₂CH₃1,1-difluoroethane HFC-227ca CF₃CF₂CHF₂ 1,1,1,2,2,3,3-heptafluoropropaneHCFC-233ab CF₃CCl₂CH₂Cl 1,2,2-trichloro-3,3,3-trifluoropropaneHCFC-234ab CF₃CCl₂CH₂F 2,2-dichloro-1,1,1,3-tetrafluoropropane HFC-236faCF₃CH₂CF₃ 1,1,1,3,3,3-hexafluoropropane HCFC-243fa CF₃CH₂CHCl₂3,3-dichloro-1,1,1-trifluoropropane HCFC-243db CF₃CHClCH₂Cl2,3-dichloro-1,1,1-trifluoropropane HCFC-244bb CF₃CFClCH₃2-chloro-1,1,1,2-tetrafluoropropane HCFC-244db CF₃CHClCH₂F2-chloro-1,1,1,3-tetrafluoropropane HFC-245fa CF₃CH₂CHF₂1,1,1,3,3-pentafluoropropane HFC-245cb CF₃CF₂CH₃1,1,1,2,2-pentafluoropropane HFC-245eb CF₃CHFCH₂F1,1,1,2,3-pentafluoropropane HCFC-253fb CF₃CH₂CH₂Cl3-chloro-1,1,1-trifluoropropane HFC-254fb CF₃CH₂CH₂F1,1,1,3-tetrafluoropropane HCO-1130 CHCl═CHCl E- and/orZ-1,2-dichloroethene HCO-1130a CCl₂═CH₂ 1,1-dichloroethene HCFC-1131CHF═CHCl E- and/or Z-1-chloro-2-fluoroethene HFO-1141 CHF═CH₂fluoroethene HCFO-1223xd CF₃CCl═CHCl 1,2-difluoro-3,3,3-trifluoropropeneHCFO-1233zd CF₃CH═CHCl E- and/or Z-1-chloro-3,3,3- trifluoropropeneHCFO-1233xf CF₃CCl═CH₂ 2-chloro-1,1,1-trifluoropropene HFO-1234yfCF₃CF═CH₂ 2,3,3,3-tetrafluoropropene HFO-1234ze CF₃CH═CHF E- and/orZ-1,3,3,3-tetrafluoropropene HCFO-1242zf CClF₂CH═CH₂3-chloro-3,3-difluoropropene HFO-1243zf CF₃CH═CH₂ 1,1,1-trifluoropropene(TFP) HFO-1336 C₄H₂F₆ E- and/or Z-hexafluorobutene

HCFC-243db, HCFO-1233xf, and HCFC-244bb are available from specialtychemical manufacturers, including SynQuest Laboratories, Inc. (Alachua,Fla., U.S.A.) or may be made as described herein. For instance,HCFC-243db, HCFO-1233xf, and HCFC-244bb may be prepared by non-catalyticchlorination of HFO-1243zf, as described in International PatentApplication Publication No. WO2008/054782, published May 8, 2008. Also,HCFO-1233xf and HCFC-244bb may be prepared by catalytic fluorination of243db as described in International Patent Application Publication No.WO2008/054781, published May 8, 2008. The additional compounds presentin each disclosed composition will depend upon the method ofmanufacture.

In some embodiments, certain precursor compounds to HCFC-243db,HCFO-1233xf, or HCFC-244bb contain impurities that then appear asadditional compounds in the described compositions. In otherembodiments, these precursor compounds may themselves react during the243db formation to form additional compounds that then appear in theHCFC-243db compositions. In other embodiments, the reaction conditionsunder which the HCFC-243db, HCFO-1233xf, or HCFC-244bb are produced alsoproduce by-products, by which is meant adventitious reaction pathwaysmay occur simultaneously to produce compounds other than HCFC-243db,HCFO-1233xf or HCFC-244bb and the quantity and identity of theseadditional compounds will depend upon the particular conditions underwhich the HCFC-243db, HCFO-1233xf or HCFC-244bb are produced.

In one embodiment, HFO-1234yf may be produced in a single step fromHCFC-243db. In another embodiment, the reaction sequence may be carriedout in a step-wise manner. In another embodiment, HCFO-1233xf may beproduced from HCFC-243db and then HCFO-1233xf may be converted directlyto HFO-1234yf. In yet another embodiment, HCFC-244bb may be producedfrom HCFC-243db and then the HCFC-244bb may be converted to HFO-1234yf.

Fluorochlorination of HFO-1243zf

In some embodiments, HFO-1243zf may be used to make HCFC-243db,HCFO-1233xf, HCFC-244db, and/or HFO-1234yf by fluorochlorination.HFO-1243zf is commercially available from E.I. DuPont de Nemours andCompany (Wilmington, Del., USA).

The fluorochlorination reaction may be carried out in the liquid orvapor phase. For liquid phase embodiments of the invention, the reactionof HFO-1243zf with HF and Cl₂ may be conducted in a liquid-phase reactoroperating in batch, semi-batch, semi-continuous, or continuous modes. Inthe batch mode, HFO-1243zf, Cl₂, and HF are combined in an autoclave orother suitable reaction vessel and heated to the desired temperature.

In one embodiment, this reaction is carried out in semi-batch mode byfeeding Cl₂ to a liquid-phase reactor containing HF and HFO-1243zf or byfeeding HFO-1243zf and Cl₂ to a liquid-phase reactor containing HF, orby feeding Cl₂ to a mixture containing HF and reaction products formedby initially heating HFO-1243zf and HF. In another embodiment, HF andCl₂ may be fed to a liquid-phase reactor containing a mixture ofHFO-1243zf and reaction products formed by reacting HF, Cl₂, andHFO-1243zf. In another embodiment of the liquid-phase process, HF, Cl₂,and HFO-1243zf may be fed concurrently in the desired stoichiometricratio to the reactor containing a mixture of HF and reaction productsformed by reacting HF, Cl₂, and HFO-1243zf.

Suitable temperatures for the reaction of HF and Cl₂ with HFO-1243zf inthe liquid-phase reactor are, in one embodiment, from about 80° C. toabout 180° C., and in another embodiment, from about 100° C. to about150° C. Higher temperatures typically result in greater conversion ofthe HFO-1243zf.

A suitable molar ratio of HF to total amount of HFO-1243zf fed to theliquid-phase reactor is, in one embodiment, at least stoichiometric andin another embodiment, is from about 5:1 to about 100:1. Of note areembodiments wherein the molar ratio of HF to HFO-1243zf is from about8:1 to about 50:1. A suitable molar ratio of Cl₂ to total amount ofHFO-1243zf fed to the liquid-phase reactor is from about 1:1 to about2:1.

The reactor pressure in the liquid-phase process is not critical and inbatch reactions is usually the autogenous pressure of the system at thereaction temperature. The pressure of the system increases as hydrogenchloride is formed by replacement of hydrogen substituents by chlorine,and by replacement of chlorine substituents by fluorine in the startingmaterials and intermediate reaction products. In a continuous process itis possible to set the pressure of the reactor in such a way that thelower boiling products of the reaction, such as HCl, HFO-1234yf(CF₃CF═CH₂), E/Z-1234ze (E/Z-CF₃CH═CHF), and HFC-245cb (CF₃CF₂CH₃), arevented from the reactor, optionally through a packed column orcondenser. In this manner, higher boiling intermediates remain in thereactor and the volatile products are removed. Typical reactor pressuresare from about 20 psig (239 kPa) to about 1,000 psig (6,994 kPa).

In some embodiments, in which the reaction is conducted using aliquid-phase process, catalysts which may be used include carbon, AlF₃,BF₃, FeCl_(3-a)F_(a) (where a=0 to 3), FeX₃ supported on carbon,SbCl_(3-a)F_(a), AsF₃, MCl_(5-b)F_(b) (where b=0 to 5 and M=Sb, Nb, Ta,or Mo), and M′Cl_(4-c)F_(c) (where c=0 to 4, and M′=Sn, Ti, Zr, or Hf).In another embodiment, catalysts for the liquid phase process areMCl_(5-b)F_(b) (where b=0 to 5 and M=Sb, Nb, or Ta).

In another embodiment, the reaction of HF and Cl₂ with HFO-1243zf iscarried out in the vapor phase. Typically a heated reactor is used. Anumber of reactor configurations are possible including horizontal orvertical orientation of the reactor as well as the sequence of reactionof the HFO-1243zf with HF and Cl₂. In one embodiment of the invention,the HFO-1243zf may be initially vaporized and fed to the reactor as agas.

In another embodiment of the invention, HFO-1243zf may be contacted withHF, optionally in the presence of Cl₂, in a pre-reactor prior toreaction in the vapor-phase reactor. In one embodiment, the pre-reactormay be empty. In another embodiment, the reactor is filled with asuitable packing such as nickel-copper alloys commercially availablefrom Special Metals Corp. (New Hartford, N.Y.) under the trademarkMonel®, (hereinafter “Monel®”) nickel-based alloys commerciallyavailable from Haynes International (Kokomo, Ind.) under the trademarkHastelloy®, (hereinafter “Hastelloy®”) or other nickel alloy turnings orwool, or other material inert to HCl and HF which allows efficientmixing of HFO-1243zf and HF vapor.

Suitable temperatures for the pre-reactor in one embodiment are fromabout 80° C. to about 250° C., in another embodiment, from about 100° C.to about 200° C. Temperatures greater than about 100° C. result in someconversion of the HFO-1243zf to compounds having a higher degree offluorination. Higher temperatures result in greater conversion of theHFO-1243zf entering the reactor and a greater degree of fluorination inthe converted compounds. Under these conditions, for example, a mixtureof HF, Cl₂, and HFO-1243zf is converted to a mixture containingpredominantly HCFC-243db and HCFC-244db (CF₃CHClCH₂F).

The degree of fluorination reflects the number of fluorine substituentsthat replace chlorine substituents in the HFO-1243zf and theirchlorinated products. For example, HCFC-253fb represents a higher degreeof fluorination than HCC-250fb and HFO-1243zf represents a higher degreeof fluorination than HCO-1240zf.

The molar ratio of HF to the total amount of HFO-1243zf in thepre-reactor is in one embodiment, from about the stoichiometric ratio ofHF to the total amount of HFO-1243zf to about 50:1. In anotherembodiment, the molar ratio of HF to the total amount of HFO-1243zf inthe pre-reactor is from about twice the stoichiometric ratio of HF tothe total amount of HFO-1243zf to about 30:1. In another embodiment, themolar ratio of HF to the total amount of HFO-1243zf is present in thepre-reactor, and no additional amount of HF is added to the vapor-phasereaction zone.

In another embodiment, the HFO-1243zf may be contacted with Cl₂ in apre-reactor, optionally in the presence of HF, prior to reaction in thevapor-phase reactor.

Suitable temperatures for the pre-reactor for this embodiment of theinvention are from about 80° C. to about 250° C., preferably from about100° C. to about 200° C. Under these conditions, at least a portion ofHFO-1243zf is converted to HCFC-243db. Higher temperatures typicallyresult in a higher degree of halogenation of the HFO-1243zf.

The degree of halogenation reflects the total number of halogensubstituents (chlorine plus fluorine) in a halopropane and/orhalopropene product. For example, HFO-1234yf has a higher degree ofhalogenation (i.e., 4) than does HFO-1243zf (i.e., 3).

The molar ratio of Cl₂ to the total amount of HFO-1243zf is, in oneembodiment, from about 0.5:1 to about 2:1. In another embodiment, themolar ratio of Cl₂ to the total amount of the HFO-1243zf is from about1.1:1 to about 1:1.

In one embodiment, the HFO-1243zf is vaporized, optionally in thepresence of HF, and fed to a pre-reactor or to a vapor-phase reactoralong with HF and Cl₂.

Suitable temperatures for the vapor-phase reaction are from about 120°C. to about 500° C. Temperatures of from about 250° C. to about 350° C.favor the formation of HFO-1234yf and HFC-245cb. Temperatures of fromabout 350° C. to about 450° C. favor the formation of HFO-1234ze,HFC-245fa, and HCFO-1233zd. At temperatures of from about 250° C. toabout 450° C., some HCFO-1233xf is also produced. Higher temperaturesresult in greater conversion of HFO-1243zf and higher degrees offluorination and halogenation in the converted compounds.

Suitable reactor pressures for the vapor-phase reactor may be from about1 to about 30 atmospheres. A pressure of about 15 to about 25atmospheres may be advantageously employed to facilitate separation ofHCl from other reaction products, and the suitable reaction time mayvary from about 1 to about 120 seconds, preferably from about 5 to about60 seconds.

The molar ratio of HF to the total amount of HFO-1243zf for thevapor-phase reaction is, in one embodiment, from about thestoichiometric ratio of HF to the total amount of HFO-1243zf to about50:1 and, in another embodiment, from about 10:1 to about 30:1.

In one embodiment, a catalyst is used in the reaction zone for thevapor-phase reaction of HF and Cl₂ with HFO-1243zf. Chlorofluorinationcatalysts which may be used in the vapor phase reaction include carbon;graphite; alumina; fluorided alumina; aluminum fluoride; aluminasupported on carbon; aluminum fluoride supported on carbon; fluoridedalumina supported on carbon; magnesium fluoride supported on aluminumfluoride; metals (including elemental metals, metal oxides, metalhalides, and/or other metal salts); metals supported on aluminumfluoride; metals supported on fluorided alumina; metals supported onalumina; and metals supported on carbon; mixtures of metals.

Suitable metals for use as catalysts (optionally supported on alumina,aluminum fluoride, fluorided alumina, or carbon) include chromium, iron,cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium,platinum, manganese, rhenium, scandium, yttrium, lanthanum, titanium,zirconium, and hafnium, copper, silver, gold, zinc, and/or metals havingan atomic number of 58 through 71 (i.e., the lanthanide metals). In oneembodiment, when used on a support, the total metal content of thecatalyst will be from about 0.1 to about 20 percent by weight based onthe total weight of the catalyst; in another embodiment from about 0.1to about 10 percent by weight based on the total weight of the catalyst.

Suitable chlorofluorination catalysts for the vapor-phase reactionsinclude chromium-containing catalysts including chromium(III) oxide(Cr₂O₃); Cr₂O₃ with other metals such as magnesium halides or zinchalides supported on Cr₂O₃; chromium(III) halides supported on carbon;mixtures of chromium and magnesium (including elemental metals, metaloxides, metal halides, and/or other metal salts) optionally supported ongraphite; and mixtures of chromium and other metals (including elementalmetals, metal oxides, metal halides, and/or other metal salts)optionally supported on graphite, alumina, or aluminum halides such asaluminum fluoride.

Chromium-containing catalysts are well known in the art. They may beprepared by either precipitation methods or impregnation methods asgenerally described by Satterfield on pages 87-112 in HeterogeneousCatalysis in Industrial Practice, 2^(nd) edition (McGraw-Hill, New York,1991).

Of note are chlorofluorination catalysts that comprise at least onechromium-containing component selected from the group consisting ofcrystalline alpha-chromium oxide where from about 0.05 atom % to about 6atom % of the chromium atoms in the alpha-chromium oxide lattice arereplaced by trivalent cobalt atoms, and crystalline alpha-chromium oxidewhere from about 0.05 atom % to about 6 atom % of the chromium atoms inthe alpha-chromium oxide lattice are replaced by trivalent cobalt atomswhich has been treated with a fluorinating agent. These catalysts,including their preparation, have been disclosed in U.S. PatentApplication Publication US2005/0228202.

Optionally, the metal-containing catalysts described above can bepretreated with HF. This pretreatment can be accomplished, for example,by placing the metal-containing catalyst in a suitable container, andthereafter, passing HF over the metal-containing catalyst. In oneembodiment, such container can be the reactor used to perform thechlorofluorination reaction. In one embodiment, the pretreatment time isfrom about 15 to about 300 minutes, and the pretreatment temperature isfrom about 200° C. to about 450° C.

In one embodiment, the product mixture comprises HFC-245cb, HFC-245fa,HFO-1234yf, HFO-1234ze, HCFO-1233zd and HCFO-1233xf.

In one embodiment, halopropane by-products that may be formed in thechlorofluorination reactions having higher degrees of halogenationand/or fluorination than pentafluoropropanes include CF₃CCl₂CF₃(CFC-216aa), CF₃CClFCClF₂ (CFC-216ba), CF₃CClFCF₃ (CFC-217ba),CF₃CF₂CClF₂ (CFC-217ca), CF₃CHFCF₃(HFC-227ea), CF₃CF₂CHF₂ (HFC-227ca),CF₃CClFCHF₂ (HCFC-226ba), CF₃CF₂CHClF (HCFC-226ca), CF₃CHClCF₃(HCFC-226da), CF₃CCl₂CHF₂ (HCFC-225aa), CF₃CClFCHClF (HCFC-225ba),CF₃CF₂CHCl₂ (HCFC-225ca), CF₃CCl₂CClF₂ (CFC-215aa), CF₃CClFCCl₂F(CFC-215bb), CF₃CCl₂CCl₂F (HCFC-214ab), CF₃CCl₂CHClF (HCFC-224aa), andCF₃CClFCHCl₂ (HCFC-224ba).

In one embodiment, halopropene by-products that may be formed in thechlorofluorination reactions having a higher degree of halogenation thantetrafluoropropenes include CF₃CCl═CHCl (HCFO-1223xd).

In one embodiment, the product comprises HCFC-243db and at least oneadditional compound selected from the group consisting of ethylene,HFC-23, CFC-13, HFC-143a, HFC-152a, HFO-1234yf, HFO-1243zf, HFC-236fa,HCO-1130, HCO-1130a, HFO-1234ze, HFO-1336, HCFC-244db, HFC-245fa,HFC-245cb, HCFC-133a, HCFC-254fb, HCFC-1131, HCFO-1233xf, HCFO-1233zd,HCFO-1242zf, HCFC-253fb, HCFO-1223xd, HCFC-233ab, HCFC-226ba, andHFC-227ca.

In cases where the product mixture produced by the processes of thisinvention comprises (i) product compounds HFC-245cb, HFC-245fa,HFO-1234yf, HFO-1234ze, HCFO-1233zd and HCFO-1233xf, (ii) HF, HCl, andCl₂, (iii) higher boiling by-products such as CF₃CHClCH₂Cl (HCFC-243db),CF₃CHClCH₂F (HCFC-244bb) and (iv) chlorinated by-products such asC₃HCl₃F₄, C₃HCl₂F₅, C₃HClF₆, C₃Cl₃F₅, and C₃Cl₂F₆, the separationprocesses, such as distillation, may be employed to recover the productcompounds from such a product mixture.

Fluorination of HCFC-243db

In some embodiments, HCFC-243db may be used to make HCFC-HCFO-1233xf,HCFC-244db, and/or HFO-1234yf by fluorination. These reactions are shownin FIG. 1. The fluorination reaction may be carried out in the liquid orvapor phase. For liquid phase embodiments of the invention, the reactionof HCFC-243db with HF may be conducted in a liquid-phase reactoroperating in batch, semi-batch, semi-continuous, or continuous modes. Inthe batch mode, starting HCFC-243db and HF are combined in an autoclaveor other suitable reaction vessel and heated to the desired temperature.

In one embodiment, this reaction is carried out in semi-batch mode byfeeding HF to a liquid-phase reactor containing HCFC-243db or by feedingHCFC-243db to a liquid-phase reactor containing HF, or by feeding HF toa mixture containing HF and reaction products formed by initiallyheating HCFC-243db and HF. In another embodiment, HF may be fed to aliquid-phase reactor containing a mixture of HCFC-243db and reactionproducts formed by the reaction of HF, and HCFC-243db. In anotherembodiment of the liquid-phase process, HF, and HCFC-243db may be fedconcurrently in the desired stoichiometric ratio to the reactorcontaining a mixture of HF and reaction products formed by reacting HF,and HCFC-243db.

Suitable temperatures for the reaction of HF with HCFC-243db in theliquid-phase reactor are, in one embodiment, from about 80° C. to about180° C., in another embodiment, from about 100° C. to about 150° C.Higher temperatures typically result in greater conversion of theHCFC-243db.

A suitable molar ratio of HF to HCFC-243db fed to the liquid-phasereactor is, in one embodiment, at least stoichiometric and, in anotherembodiment, is from about 5:1 to about 100:1. Of note are embodimentswherein the molar ratio of HF to HCFC-243db is from about 8:1 to about50:1.

The reactor pressure in the liquid-phase process is not critical and inbatch reactions is usually the autogenous pressure of the system at thereaction temperature. The pressure of the system increases as hydrogenchloride is formed by replacement of chlorine substituents by fluorinein the HCFC-243db and intermediate reaction products. In a continuousprocess it is possible to set the pressure of the reactor in such a waythat the lower boiling products of the reaction, such as HCl, CF₃CF═CH₂,and E/Z-CF₃CH═CHF, are vented from the reactor, optionally through apacked column or condenser. In this manner, higher boiling intermediatesremain in the reactor and the volatile products are removed. Typicalreactor pressures are from about 20 psig (239 kPa) to about 1,000 psig(6,994 kPa).

In embodiments in which the reaction is conducted using a liquid-phaseprocess, catalysts which may be used include carbon, AlF₃, BF₃,FeCl_(3-a)F_(a) (where a=0 to 3), FeX₃ supported on carbon,SbCl_(3-a)F_(a), AsF₃, MCl_(5-b)F_(b) (where b=0 to 5 and M=Sb, Nb, Ta,or Mo), and M′Cl_(4-c)F_(c) (where c=0 to 4, and M′=Sn, Ti, Zr, or Hf).In one embodiment, catalysts for the liquid phase process areMCl_(5-b)F_(b) (where b=0 to 5 and M=Sb, Nb, or Ta).

In one embodiment, the reaction of HF with HCFC-243db is carried out inthe vapor phase. Typically a heated reactor is used. A number of reactorconfigurations are possible including horizontal or vertical orientationof the reactor as well as the sequence of reaction of the startingmaterials with HF. In one embodiment, the HCFC-243db may be initiallyvaporized and fed to the reactor as a gas.

In another embodiment of the invention, the HCFC-243db may be contactedwith HF in a pre-reactor prior to reaction in the vapor-phase reactor.The pre-reactor may be empty, but is preferably filled with a suitablepacking such as nickel-copper alloys commercially available from SpecialMetals Corp. (New Hartford, N.Y.) under the trademark Monel®,nickel-based alloys such as Hastelloy®, or other nickel alloy turningsor wool, or other material inert to HCl and HF which allows efficientmixing of HCFC-243db and HF vapor.

Suitable temperatures for the pre-reactor in one embodiment are fromabout 80° C. to about 250° C., in another embodiment, from about 100° C.to about 200° C. Temperatures greater than about 100° C. result in someconversion of the HCFC-243db to compounds having a higher degree offluorination. Higher temperatures result in greater conversion of theHCFC-243db entering the reactor and a greater degree of fluorination inthe converted compounds. Under these conditions, for example, a mixtureof HF and HCFC-243db is converted to a mixture containing predominantlyHF, HCl, HCFC-243db, HCFC-244db (CF₃CHClCH₂F), and HCFO-1233xf.

The degree of fluorination reflects the number of fluorine substituentsthat replace chlorine substituents in the HCFC-243db and theirfluorinated products. For example, HFO-1234yf represents a higher degreeof fluorination than HCFO-1233xf.

The molar ratio of HF to the total amount of HCFC-243db in thepre-reactor is, in one embodiment, from about the stoichiometric ratioof HF to the total amount of HCFC-243db to about 50:1. In anotherembodiment, the molar ratio of HF to the total amount of HCFC-243db inthe pre-reactor is from about twice the stoichiometric ratio of HF tothe total amount of HCFC-243db to about 30:1. In another embodiment, themolar ratio of HF to the amount of HCFC-243db is present in thepre-reactor, and no additional amount of HF is added to the vapor-phasereaction zone.

In one embodiment, the HCFC-243db and HF are vaporized and fed to apre-reactor or to a vapor-phase reactor.

Suitable temperatures for the vapor-phase reaction are from about 120°C. to about 500° C. Temperatures in the range of from about 300° C. toabout 350° C. favor the formation of HFO-1234yf and HFC-245cb andHCFO-1233xf. Temperatures in the range of from about 350° C. to about450° C. favor the additional formation of HFO-1234ze, HFC-245fa, andHCFO-1233zd. Higher temperatures result in greater conversion ofHCFC-243db and greater degrees of fluorination in the convertedproducts. Reactor temperatures of from about 150° C. to about 275° C.favor the formation of HCFO-1233xf as the major product.

Suitable reactor pressures for the vapor-phase reactor may be from about1 to about 30 atmospheres. A pressure of about 15 to about 25atmospheres may be advantageously employed to facilitate separation ofHCl from other reaction products, and the suitable reaction time mayvary from about 1 to about 120 seconds, preferably from about 5 to about60 seconds.

The molar ratio of HF to the amount of HCFC-243db for the vapor-phasereaction is, in one embodiment, from about the stoichiometric ratio ofHF to the amount of HCFC-243db to about 50:1 and, in another embodiment,from about 10:1 to about 30:1.

In some embodiments, a catalyst is used in the reaction zone for thevapor-phase reaction of HF with HCFC-243db. Fluorination catalysts whichmay be used in the vapor phase reaction include carbon; graphite;alumina; fluorided alumina; aluminum fluoride; alumina supported oncarbon; aluminum fluoride supported on carbon; fluorided aluminasupported on carbon; magnesium fluoride supported on aluminum fluoride;metals (including elemental metals, metal oxides, metal halides, and/orother metal salts); metals supported on aluminum fluoride; metalssupported on fluorided alumina; metals supported on alumina; and metalssupported on carbon; mixtures of metals.

Suitable metals for use as catalysts (optionally supported on alumina,aluminum fluoride, fluorided alumina, or carbon) include chromium, iron,cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium,platinum, manganese, rhenium, scandium, yttrium, lanthanum, titanium,zirconium, and hafnium, copper, silver, gold, zinc, and/or metals havingan atomic number of 58 through 71 (i.e., the lanthanide metals). In someembodiments, when used on a support, the total metal content of thecatalyst will be from about 0.1 to about 20 percent by weight based onthe total weight of the catalyst; in another embodiment, from about 0.1to about 10 percent by weight based on the total weight of the catalyst.

Typical fluorination catalysts for the vapor-phase reactions in thisinvention include chromium-containing catalysts including chromium(III)oxide (Cr₂O₃); Cr₂O₃ with other metals such as magnesium halides or zinchalides supported on Cr₂O₃; chromium(III) halides supported on carbon;mixtures of chromium and magnesium (including elemental metals, metaloxides, metal halides, and/or other metal salts) optionally supported ongraphite; and mixtures of chromium and other metals (including elementalmetals, metal oxides, metal halides, and/or other metal salts)optionally supported on graphite, alumina, or aluminum halides such asaluminum fluoride.

Chromium-containing catalysts are well known in the art. They may beprepared by either precipitation methods or impregnation methods asgenerally described by Satterfield on pages 87-112 in HeterogeneousCatalysis in Industrial Practice, 2nd edition (McGraw-Hill, New York,1991).

Of note are fluorination catalysts that comprise at least onechromium-containing component selected from the group consisting ofcrystalline alpha-chromium oxide where from about 0.05 atom % to about 6atom % of the chromium atoms in the alpha-chromium oxide lattice arereplaced by trivalent cobalt atoms, and crystalline alpha-chromium oxidewhere from about 0.05 atom % to about 6 atom % of the chromium atoms inthe alpha-chromium oxide lattice are replaced by trivalent cobalt atomswhich has been treated with a fluorinating agent. These catalysts,including their preparation, have been disclosed in U.S. PatentApplication Publication US2005/0228202.

Optionally, the metal-containing catalysts described above can bepretreated with HF. This pretreatment can be accomplished, for example,by placing the metal-containing catalyst in a suitable container, andthereafter, passing HF over the metal-containing catalyst. In oneembodiment of this invention, such container can be the reactor used toperform the fluorination reaction in this invention. Typically, thepretreatment time is from about 15 to about 300 minutes, and thepretreatment temperature is from about 200° C. to about 450° C.

In one embodiment of this invention, the product mixture comprisesHFC-245cb, HFC-245fa, HFO-1234yf, HFO-1234ze, HCFO-1233zd andHCFO-1233xf.

Fluorination of HCFO-1233xf

In some embodiments, HCFO-1233xf may be used to make HCFC-HCFC-244bb,and/or HFO-1234yf by fluorination. These reactions are shown in FIG. 1.

In one embodiment, the reaction of HCFO-1233xf to HCFC-244bb may becarried out in the liquid phase. In another embodiment, the reaction maybe carried out in the vapor phase.

In one embodiment, the reaction of HCFO-1233xf to HCFC-244bb may becarried out in batch mode. In another embodiment, the reaction may becarried out in a continuous mode.

In one embodiment, a liquid phase reaction of HCFO-1233xf to HCFC-244bbmay be carried out in the presence of a catalyst. In one embodiment, thecatalyst may be a Lewis acid catalyst. In one embodiment, the catalystmay be a metal-halide catalyst. In another embodiment, the catalyst maybe at least one catalyst selected from the group consisting of antimonyhalides, tin halides, thallium halides, iron halides and combinations oftwo or more thereof. In another embodiment, the catalysts may be atleast one catalyst selected from antimony pentachloride (SbCl₅),antimony trichloride (SbCl₃), antimony pentafluoride (SbF₅), tintetrachloride (SnCl₄), titanium tetrachloride (TiCl₄), iron trichloride(FeCl₃, and combinations thereof. In some embodiments, the reaction maybe carried out with any known fluorination catalyst for liquid phasereactions.

In one embodiment, the reaction of HCFO-1233xf to HCFC-244bb may becarried out in the absence of catalyst.

In one embodiment, a vapor phase reaction of HCFO-1233xf to HCFC-244bbmay be carried out in the presence of a catalyst. In one embodiment, thereaction is carried out in the presence of a chromium-based catalyst, aniron-based catalyst, or combinations thereof. In one embodiment, thechromium based catalyst is a chromium oxide (e.g. Cr₂O₃). In oneembodiment, the iron-based catalyst may be FeCl₃ on carbon.

In one embodiment, the vapor phase reaction of HCFO-1233xf to HCFC-244bbis carried out in the absence of catalyst.

Dehydrochlorination of HCFC-244bb

In some embodiments, dehydrochlorination of HCFC-244bb is used toprepare HFO-1234yf.

In one embodiment, dehydrochlorination of HCFC-244bb to HFO-1234yf iscarried out in the vapor phase.

In one embodiment, vapor phase dehydrochlorination is carried out in thepresence of catalyst. In one embodiment, the catalyst is selected fromcarbon and/or metal based catalysts. In one embodiment, the catalyst maybe selected from an activated carbon, a nickel-based catalyst, apalladium based catalyst, or any combination of these catalysts. In oneembodiment, the catalyst may be selected from the group consisting ofNi-mesh, palladium on carbon, palladium on aluminum oxide, orcombinations thereof.

In one embodiment, HFO-1234yf is prepared by thermal dehydrochlorinationof HCFC-244bb. In one embodiment, this reaction occurs in the absence ofa catalyst. In one embodiment, HCFC-244bb is introduced into a reactionvessel which temperature is maintained at a temperature high enough toeffect the thermal dehydrochlorination of HCFC-244bb. In one embodiment,the temperature is high enough to effect the thermal dehydrochlorinationof HCFC-244bb to a percent conversion of at least 50%. In anotherembodiment, the temperature is high enough to effect the thermaldehydrochlorination of HCFC-244bb to a percent conversion of at least65%. In yet another embodiment, the temperature is high enough to effectthe thermal dehydrochlorination of HCFC-244bb to a percent conversion ofat least 80%. In yet another embodiment, the temperature is high enoughto effect the thermal dehydrochlorination of HCFC-244bb to a percentconversion of at least 70% for at least 12 hours of continuousoperation.

In one embodiment, HCFC-244bb is introduced into a reaction vessel intoa reaction vessel which temperature is maintained at a temperature inthe range of from about 500° C. to about 700° C. In another embodiment,the temperature of the reaction vessel is maintained in the range fromabout 500° C. to about 650° C. In yet another embodiment, thetemperature of the reaction vessel is maintained at a temperature highenough to effect the pyrolysis of HCFC-244bb to HFO-1234yf with aselectivity of 80% or greater. In yet another embodiment, thetemperature of the reaction vessel is maintained at a temperature highenough to effect the pyrolysis of HCFC-244bb to HFO-1234yf with aselectivity of 85% or greater.

In one embodiment, the reaction zone is a reaction vessel comprised ofmaterials which are resistant to corrosion. In one embodiment, thesematerials comprise alloys, such as nickel-based alloys such asHastelloy®, nickel-chromium alloys commercially available from SpecialMetals Corp. under the trademark Inconel® (hereinafter “Inconel®”) ornickel-copper alloys commercially available from Special Metals Corp.(New Hartford, N.Y.) under the trademark Monel®, or vessels havingfluoropolymers linings.

In one embodiment, the HCFC-244bb is preheated in a vaporizer to atemperature of from about 30° C. to about 100° C. In another embodiment,the HCFC-244bb is preheated in a vaporizer to a temperature of fromabout 30° C. to about 80° C.

In some embodiments, an inert diluent gas is used as a carrier gas forHCFC-244bb. In one embodiment, the carrier gas is selected is nitrogen,argon, helium or carbon dioxide.

Without further elaboration, it is believed that one skilled in the artcan, using the description herein, utilize the present invention to itsfullest extent. The following specific embodiments are, therefore, to beconstrued as merely illustrative, and do not constrain the remainder ofthe disclosure in any way whatsoever.

EXAMPLES

General Procedure for Product Analysis

The following general procedure is illustrative of the method used foranalyzing the products of fluorination reactions. Part of the totalreactor effluent was sampled on-line for organic product analysis usinga gas chromatograph equipped with a mass selective detector (GC/MS). Thegas chromatography utilized a 20 ft. (6.1 m) long×⅛ in. (0.32 cm)diameter tube containing perfluorinated polyether sold under thetrademark Krytox® by E. I. du Pont de Nemours and Company (hereinafter“DuPont”) of Wilmington, Del. on an inert carbon support. The heliumflow was 30 mL/min (5.0×10⁻⁷ m³/sec). Gas chromatographic conditionswere 60° C. for an initial hold period of three minutes followed bytemperature programming to 200° C. at a rate of 6° C./minute.

Preparation of 98% Chromium/2% Cobalt Catalyst

A solution of 784.30 grams Cr(NO₃)₃[9(H₂O)] (1.96 moles) and 11.64 gramsCo(NO₃)₂[6(H₂O)] (0.040 mole) was prepared in 2000 mL of deionizedwater. The solution was treated dropwise with 950 mL of 7.4 M aqueousammonia until the pH reached about 8.5. The slurry was stirred overnightat room temperature and then evaporated to dryness in air at 110-120° C.The dried catalyst was then calcined in air at 400° C. for 24 hoursprior to use.

Legend

243db is CF₃CHClCH₂Cl 244db is CF₃CHClCH₂F 245cb is CF₃CF₂CH₃ 245fa isCF₃CH₂CHF₂ 1234yf is CF₃CF═CH₂ 1233xf is CF₃CCl═CH₂ 1243zf is CH₂═CHCF₃233ab is CF₃CCl₂CH₂Cl 1233zd is E- and/or Z-CHCl═CHCF₃ 226ba isCF₃CClFCHF₂ 1234ze is E- and/or Z-CHF═CHCF₃ 227ca is CF₃CF₂CHF₂ 1223xdis E- and/or Z-CF₃CCl═CHCl 244bb is CF₃CFClCH₃ 1141 is CHF═CH₂

Examples 1-6 Chlorofluorination of HFO-1243zf

The 98% chromium/2% cobalt catalyst prepared above (21.4 grams, 15 mL,−12 to +20 mesh, (1.68 to 0.84 mm)) was placed in a ⅝″ (1.58 cm)diameter Inconel® (Special Metals Corp. (New Hartford, N.Y.)) nickelalloy reactor tube heated in a fluidized sand bath. The catalyst waspre-fluorinated by treatment with HF as follows. The catalyst was heatedfrom 45° C. to 175° C. in a flow of nitrogen (50 cc/min) over the courseof about 1.5 hours. HF was then admitted to the reactor at a flow rateof 50 cc/min for 1.3 hours at a temperature of 175° C. The reactornitrogen flow was decreased to 20 cc/min and the HF flow increased to 80cc/min; this flow was maintained for 0.3 hour. The reactor temperaturewas then gradually increased to 400° C. over 1 hour. After this period,the HF and nitrogen flow was stopped and the reactor brought to thedesired operating temperature. A flow of HF vapor, HFO-1243zf, and Cl₂then started through the reactor. Part of the reactor effluent wasanalyzed by on line GC/MS.

The results of the chlorofluorination of HFO-1243zf over the 98/2 Cr/Cocatalyst at various operating temperatures and indicated molar ratios ofHF, HFO-1243zf and Cl₂ are shown in Table 2; analytical data is given inunits of GC area %. The nominal catalyst bed volume was 15 cc; thecontact time (CT) was 15 seconds. Examples 1 and 2 were carried out inthe absence of the catalyst.

TABLE 2 Chlorofluorination of HFO-1243zf (Part A) Ex. HF/1243/Cl₂ T, No.Ratio ° C. 1243zf 243db 244db 1234yf 245cb 1233xf 1  10/1/4 140 3.0 54.29.8 5.7 0 1.4 2^(a) 10/1/1 140 31.3 46.2 11.8 2.8 0 1.5 3^(b) 10/1/1 3005.9 0 0 5.9 22.2 30.7 4^(c) 10/1/4 325 0 0 0 0 0 0 5  10/1/1 350 9.1 0 011.3 11.3 25.2 6  10/1/1 375 12.8 0 0 11.6 6.3 20.6 (Part B) Ex.HF/1243/Cl₂ T, No. Ratio ° C. 1233zd 1234ze 245fa 1223xd 233ab 226ba227ca 1  10/1/4 140 7.7 — — 1.0 6.3 0 0 2^(a) 10/1/1 140 1.4 — — 0 1.3 00 3^(b) 10/1/1 300 4.1 2.1 1.3 20.2 0 0 0 4^(c) 10/1/4 325 0 0 0 0 023.8 13.9 5  10/1/1 350 12.4 4.7 1.9 18.1 0 0.2 0 6  10/1/1 375 17.6 6.52.3 16.1 0 0.2 0 ^(a)243db and 244db confirmed by ¹H and ¹⁹F NMR.^(b)245cb and 1233xf confirmed by ¹H and ¹⁹F NMR. ^(c)Additionalproducts were 215aa, 216aa, 216ba, 225aa, 225ba, 226ca, 226da.

Examples 7-11 Fluorination of HCFC-243db

The 98% chromium/2% cobalt catalyst prepared above (21.4 grams, 15 mL,−12 to +20 mesh, (1.68 to 0.84 mm)) was placed in a ⅝″ (1.58 cm)diameter Inconel® nickel alloy reactor tube heated in a fluidized sandbath. The catalyst was pre-fluorinated by treatment with HF as follows.The catalyst was heated from 45° C. to 175° C. in a flow of nitrogen (50cc/min) over the course of about 1.5 hours. HF was then admitted to thereactor at a flow rate of 50 cc/min for 1.3 hours at a temperature of175° C. The reactor nitrogen flow was decreased to 20 cc/min and the HFflow increased to 80 cc/min; this flow was maintained for 0.3 hour. Thereactor temperature was then gradually increased to 400° C. over 1 hour.After this period, the HF and nitrogen flow was stopped and the reactorbrought to the desired operating temperature. A flow of HF vapor andHCFC-243db (CF₃CHClCH₂Cl) was then started through the reactor. Part ofthe reactor effluent was analyzed by on line GC/MS.

The results of the fluorination of HFC-243db over the 98/2 Cr/Cocatalyst at various operating temperatures and indicated molar ratios ofHF and HCFC-243db are shown in Table 3; analytical data is given inunits of GC area %. The nominal catalyst bed volume was 15 cc; thecontact time (CT) was 15 seconds. Example 7 was carried out in theabsence of the catalyst.

TABLE 3 Fluorination of HCFC-243db Ex. HF/243 Temp. No. Ratio (° C.)1243zf 243db 244db 1234yf 245cb 1233xf 1233zd 1234ze 245fa 7  5/1 1400.1 88.4 7.4 0 0 3.9 0 0 0 8 10/1 275 0 0.2 0.6 1.3 4.8 90.0 0 0.7 1.0 920/1 325 0 0 0 19.1 11.4 61.7 2.3 3.1 1.9 10 20/1 350 0 0 0 32.2 8.145.3 4.7 7.9 0.9 11 20/1 400 0 0 0 17.9 6.6 36.3 19.7 14.4 3.6

Example 12 Reaction of HFC-243db with HF in the Presence of TaF₅

A 210 mL Hastelloy® C tube was charged with 10.0 grams (0.0599 mole) ofHCFC-243db and 25.4 grams (0.040 mole) of tantalum pentafluoride. Thetube was then charged with 40.0 grams (2.0 moles) of hydrogen fluoride.The tube was warmed to 150° C. and held at 149° C. to 150° C. for eighthours with shaking. The tube was then cooled to room temperature andtreated with 100 mL of water. The contents of the tube were dischargedand a small organic layer was collected and neutralized. The sample was91.1% unconverted HCFC-243db; the GC-MS analysis of the convertedproducts were as follows:

TABLE 4 Component GC Area % HFC-245cb 39.3 HFC-245fa 5.5 C₃H₃ClF₄ 9.2C₃H₃ClF₄ 27.6 HCFC-253fb 2.9 HCFC-234ab 8.6 HCFC-243fa 6.9

Example 13 Fluorination of HCFO-1233xf to HCFC-244bb

The contents of a small PTFE vial containing 20 grams of viscous SbF₅were poured into a dry 400 mL Hastelloy® shaker tube. The tube wasclosed and was pressurized with nitrogen for leak testing. The shakertube was then cooled to less than −40° C. with dry ice, slowly vented,and then evacuated. 75 grams (3.75-moles) of anhydrous HF was condensedinto the shaker tube followed by 165 grams (1.26-moles) of HCFO-1233xf.The shaker tube was placed in a barricade and shaking was started.

The shaker tube was agitated at ambient temperature (˜20-23° C.) and thepressure was 21 to 25 psig. After 2 hours, shaking was stopped and 150mL of water was carefully pumped into the shaker tube. The tube was leftovernight and then cooled to 0 to 5° C. in an ice bath beforedepressurization and transferring the contents to a plastic container.The container was kept on ice.

The container contents were poured into a polypropylene separatoryfunnel containing some ice. The lower organic layer was light amber inappearance. The organic layer was separated into a media bottle made ofa glass sold under the trademark of Pyrex® by Corning (Lowell, Mass.)(hereinafter “Pyrex®”) containing ˜50-mL of 4 molar (pH 7) phosphatebuffer and ice (˜100-mL). The organic layer was again separated andpoured into a dry Pyrex® media bottle containing a small amount ofanhydrous magnesium sulfate. Crude yield was 164.3 grams (about 120-mL,86%).

GC/MS of the crude material showed that it was mostly HCFC-244bb. Othercomponents included 0.13% 245cb, 0.09% 245eb, 0.16% 1233xf, and otherbyproducts totaling 12.2%.

Example 14 Fluorination of HCFO-1233xf to HCFC-244bb

The contents of a small PTFE vial containing 20 grams of viscous SbF₅were poured into a dry 400-mL Hastelloy® shaker tube. The tube wasclosed and was pressurized with nitrogen for leak testing. The shakertube was then cooled to less than −40° C. with dry ice, slowly vented,and then evacuated. 53 grams (2.65 moles) of anhydrous HF wastransferred into the shaker tube followed by 227 grams (1.74 moles) ofHCFO-1233xf was condensed into the chilled shaker tube. The shaker tubewas placed in the barricade and shaking was started.

The shaker tube was agitated at ambient temperature (˜18-21° C.) and thepressure was 16 to 20 psig. After 2 hours, shaking was stopped and 100mL of water was carefully pumped into the shaker tube. The tube was leftovernight and cooled to 0 to 5° C. in an ice bath before venting andtransferring the contents to a plastic container. The container was kepton ice.

The container contents were poured into a polypropylene separatoryfunnel containing some ice. The lower organic layer was light amber inappearance. The organic layer was separated into a Pyrex® media bottlecontaining about 50 mL of 4 molar (pH 7) phosphate buffer and ice(˜100-mL). The organic layer was again separated and poured into a dryPyrex® media bottle containing a small amount of anhydrous magnesiumsulfate. Crude yield was 238.8 grams (about 170-mL, 91%).

GC/MS of the crude material indicated that it was mostly HCFC-244bb.Other components included 0.11% HFC-245cb, 0.10% HFC-245eb, 0.26%HCFO-1233xf, and other byproducts totaling 9.7%.

Example 15

Example 15 demonstrates the conversion of HCFC-244bb(2-chloro-1,1,1,2-tetrafluoropropane) to HFO-1234yf(2,3,3,3-tetrafluoropropene) in the absence of a catalyst.

An empty Inconel® tube (½ inch OD) with a heated zone of about 12 incheswas heated to a temperature between 500° C. and 626° C., and HFC-244bbwas fed at 0.52 mL/hour through a vaporizer set at 40° C. using a N₂sweep of 2.4 sccm (4.0×10⁻⁸ m³). The reactor effluent was analyzed usingan on-line GCMS, with the results being reported in mole percent.

TABLE 5 Temp., Mole Percent ° C. 23 1141 143a 245cb 1234yf 254eb 244bb1233xf Unks 500 0.2 0.1 0.0 0.4 14.2 1.0 82.6 1.2 0.0 550 1.9 0.9 0.10.0 57.0 1.7 35.4 1.2 1.6 574 2.7 1.1 0.1 0.0 77.0 1.9 13.0 1.4 2.8 6036.8 2.4 0.2 0.0 85.0 1.4 1.3 0.7 2.2 626 6.9 2.0 0.2 0.0 82.5 0.7 0.21.4 5.9

Example 16

Example 16 demonstrates the conversion of HCFC-244bb(2-chloro-1,1,1,2-tetrafluoropropane) to HFO-1234yf(2,3,3,3-tetrafluoropropane) in the absence of a catalyst.

An empty Inconel® tube (½ inch OD) with a heated zone of about 12 incheswas heated to 575° C., and HFC-244bb was fed at 0.35 mL/hour through avaporizer set at 40° C. using a N₂ sweep of 3.6 sccm (6.0×10⁻⁸ m³). Thereactor was operated for a total of 19 hours continuously, and sampleswere taken periodically and analyzed to determine % conversion ofHFC-244bb, and selectivity to HFO-1234yf. The reactor effluent wasanalyzed using an on-line GCMS, and the data in Table 6 below is anaverage of at least two on-line injections at a given condition; thepercentages are mole percent.

TABLE 6 1223 Hours 23 1141 245cb 1234yf 254eb 244bb 1233xd (2 isomers)Unk 3 1.9 0.8 0.1 68.8 3.5 17.9 5.1 0.5 1.3 4 1.4 0.7 0.0 61.5 4.2 22.77.4 1.1 1.0 8 0.0 0.3 0.0 61.1 2.6 15.0 14.1 3.9 2.8 12 0.0 0.5 0.0 60.12.0 13.7 16.4 6.0 1.3 15 0.9 0.3 0.0 66.9 1.7 14.5 12.0 2.7 1.0 19 0.00.7 0.0 67.4 0.0 7.0 16.6 8.2 0.0

Example 17

Example 17 demonstrates the dehydrochlorination of HCFC-244bb(2-chloro-1,1,1,2-tetrafluoropropane) in the presence of an activatedcarbon catalyst.

An Inconel® tube (½ inch OD) was filled with 4 cc (1.99 gm) of acidwashed PCB Polynesian coconut shell based carbon from Calgon (6-10mesh). HFC-244bb was fed at 1.04 mL/hour through a vaporizer set at 40°C. using a N₂ sweep of 2.4 sccm (4.0×10⁻⁸ m³) giving a total contacttime of about 32 seconds while controlling the reactor temperature at400° C.

The data in Table 7 shows the reactor effluent composition in molepercent for this process run with an activated carbon catalyst to makeHFC-1234yf via HCl elimination over the period of 7 hours of operation.

TABLE 7 Hours 245cb 1234yf 245eb 1336 244bb 1233xf Unk 1 0.0 52.2 0.20.0 22.4 10.3 14.9 2 0.0 44.5 0.2 0.1 24.6 13.4 17.3 3 0.0 38.0 0.2 0.231.9 14.8 15.0 4 0.0 25.9 0.2 0.1 41.8 15.7 16.3 5 0.0 15.5 0.3 0.1 49.417.9 16.7 6 0.5 7.1 0.3 0.1 53.8 18.0 20.2 7 0.6 2.9 0.3 0.1 54.2 17.324.5

What is claimed is:
 1. A composition comprising HFO-1234yf, HFO-1234ze,HFO-1243zf and at least one additional compound selected from the groupconsisting of HCFO-1233xf, HCFC-244bb and HCFC-1131.
 2. The compositionof claim 1 containing less than about 1 weight percent of the at leastone additional compound.
 3. The composition of claim 1 wherein saidadditional compound comprises HCFO-1233xf.
 4. The composition of claim 1wherein said additional compound comprises HCFC-1131.
 5. The compositionof claim 1 wherein said additional compound further comprises HFC-143a.6. The composition of claim 1 wherein said additional compound comprisesHCFC-244bb.
 7. The composition of claim 2 wherein said additionalcompound comprises HCFO-1233xf and HCFC-1131.
 8. The composition ofclaim 7 wherein the amount of the at least one additional compound isgreater than 0 and less than about 1 weight percent.
 9. A compositioncomprising HFO-1234yf, HFO-1234ze, HFO-1243zf, HCFC-1131 and HFC-143a.10. A composition comprising HFO-1234yf, HFO-1234ze, HFO-1243zf,HCFC-1131, HFC-143a and at least one additional compound selected fromthe group consisting of HCFC-244db, HFC-245cb and HFC-245fa.
 11. Thecomposition of claim 10 wherein the amount of the at least oneadditional compound is greater than 0 and less than about 1 weightpercent.
 12. The composition of claim 11 wherein the additional compoundcomprises HCFC-244bb.
 13. The composition of claim 11 wherein theadditional compound comprises HFC-245cb.
 14. The composition of claim 11wherein the additional compound comprises HFC-245fa.
 15. A method forcarrying heat from a heat source to a heat sink wherein a mediacomprising the composition of claim 1 is used as heat transfer fluid.16. A heat transfer system comprising at least one member selected fromthe group consisting of air conditioners, freezers, refrigerators, heatpumps, water chillers, flooded evaporator chillers, direct expansionchillers, walk-in coolers, heat pumps, mobile refrigerators, mobile airconditioning units and combinations thereof, and wherein the systemcomprises a working fluid comprising the composition of claim
 1. 17. Theheat transfer system of claim 16 wherein the system comprises a mobilerefrigeration apparatus.
 18. A method for carrying heat from a heatsource to a heat sink wherein a media comprising the composition ofclaim 9 is used as heat transfer fluid.
 19. A method for carrying heatfrom a heat source to a heat sink wherein a media comprising thecomposition of claim 10 is used as heat transfer fluid.